Hydantoin esters of maleic anhydride copolymers



United States Patent C) ESTERS OF MALEIC ANHYDRIDE COPOLYMERS Albert C.Smith, Jr., Rochester, N. Y., assignor to Eastman Kodak Company,Rochester, N. Y., a corporation of New Jersey No Drawing. ApplicationJuly 7, 1954, Serial No. 441,934

12 Claims. (Cl. 260-77.5)

in themolar ratio of from 1:1 to 3:1 of (l) to (2) and wherein nrepresents an integer of from 2 to. 4' i. e. (CH2)n represents ethylene,propylene or butylene groups, m represents an integer of from 2 to 3, Rrepresents an atom of hydrogen or a methyl group, R1 represents an atomof hydrogen, a halogen atom such as chlorine or bromine, a phenyl group,a naphthyl group, a pyridyl group, a nitrile group, a carboxyl group, acarbamyl group, the groups -O-COR2, --CO-OR2, -OR2, -CONHR2, etc.,wherein R2 represents an alkyl group of from 1 to 4 carbon atoms, and Xrepresents an atom of hydrogen, an atom of chlorine, an alkyl group offrom 1 to 4 carbon atoms, e. g. methyl, ethyl, propyl, isopropyl, butyl,etc. groups, an alkoxy group containing froml to 4 carbon atoms, e. g.methoxy, butoxy, etc. groups, acetamino group, a -COOR2 group, a -SO3R2group or an group, wherein R2 is as above defined.

Typical structural units represented by above (1) include themonoethylenically unsaturated polymerizable compounds containing thegroup CH2:C such as ethyl ene, isobutylene, vinyl carboxylic esters suchas vinyl acetate, vinyl butyrate, vinyl benzoate, vinyl halides suchvinyl chloride, vinyl fluoride, vinylidene dichloride, etc., an alkylester, amide, N-alkyl substituted amide or nitrile of acrylic ormethacrylic acids such as methyl acrylate, ethyl acrylate, methylmethacrylate, acrylamide, methacrylamide, N-methyl acrylamide,N,N-dimethyl acrylamide, N-methyl methacrylamide, acrylonitrile,methacrylonitrile, vinyl alkyl ethers such as vinyl methyl ether, vinylethyl ether, etc., styrenes such as styrene,

ethoxy, propoxy,

"ice

alpha-methylstyrene, vinyl toluenes such as p-methylstyrene,p-acetaminostyrene, vinyl naphthalenes, C-vinyl pyridines, etc.

The above-defined resinous polymers of my invention are all soluble inone or more organic solvents such as dimethyl formamide, dioxane, methylcellosolve acetate, pyridine, chlorinated hydrocarbons, etc., but becomeinsoluble on exposure to light. Accordingly, they are useful for coatingfrom their solutions onto various surfaces which can then be exposed tolight to obtain insoluble and resistant coatings on such surfaces. Sincethe resinous materials of my invention are highly polymeric, suchcoatings are tough and continuous, and are especially useful for formingresist images on printing plate supports such as aluminum, zinc, copperand magnesium, and various alloys thereof. When coatings of the resinouspolymers on such supports are light exposed to a subject such as a line,half-tone or continuous tone image, the coatings are rendered insolublein organic solvents in the area of exposure, and the unexposed area canthen be readily removed with one or more of the abovementioned solvents.When sensitizing agents are incorporated into the solutions of polymer,the light sensitivity of the resulting coatings are increased and,accordingly, the exposure time of the process is decreased which is veryadvantageous. The resulting relief image of insolubilized polymer canthen be used as a plate etching resist or if prepared on a lithographicsurface of zinc, surface-hydrolyzed cellulose ester, casein, etc., therelief image can be inked and printed on a lithographic or'otherprinting press. Those of my resinous polymers consisting of copolymersof styrene and maleic anhydride, in the ratio of from 1:1 to 3:1 molarproportions of styrene to maleic anhydride, which are subsequentlyesterified with certain 3-(w-hydroxyalkyl)-5- benzal hydantoins, areespecially light-sensitive and useful for preparing the above kind ofresist images.

It is, accordingly, an object of my invention to provide a new class ofresinous polymers. A further object is to provide compositions which arelight-sensitive and particularly useful for photomechanical reproductionprocesses. Another object is to provide a process for preparing the newclass of resinous copolymers. Other objects will become apparenthereinafter.

In accordance with my invention, I prepare the resinous polymers'of theinvention by first preparing the binary polymers of maleic anhydride byconventional polymerization methods, for example, by heating, exposingto actinic light such as ultraviolet, or use of polymerization catalystssuch as benzoyl peroxide, potassium persulfate, etc., or combinations ofthese polymerization accelerators, in mass, in solution or suspensionsin water or nonsolvents, a mixture of maleic anhydride and the selectedcomonomer. The copolymers are then reacted with the selected3-(w-hydroxyalkyl)-5-benzal hydantoins to obtain the correspondinglight-sensitive resinous polymers of the invention. Preferably the aboveesterification reaction is carried out in a solvent medium such aspyridine at temperatures up to the refluxing temperature of the reactionmixture, preferably from about 30 to C. The proportions of the3-(w-hydroxyalkyl)-5-benzal hydantoin employed can vary widely from anamount appreciably less than a molecular equivalent of the maleicanhydride in the copolymer to six or more times this amount, i. e. thecomponents are present in the initial copolymers in the molar ratio offrom about 0.5 :1 to about 3:1 but preferably 1:1 of the comonomer tomaleic anhydride. The intermediate hydantoin compounds employed in theesterification reaction may be prepared by reacting ethylisocyanoacetate with an alkanolamine such as ethanolamine (Z-aminoethylalcohol), propanolamine (3-aminopropy1 alcohol) or butanolamine(4-amino-nbutyl-alcohol) to obtain the corresponding N--hydroxyalkyl-N-carbe'thoxymethyl urea which may then be treated with anaqueous acid such as 6-normal hydrochloric acid to cause ring closure togive the corresponding 3-(whydroxyalkyl) hydantoin. The latter compoundsare then reacted with suitable aromatic aldehydes of the benzene seriesrepresented by the general formula CHO wherein m and X have thepreviously defined meanings, for example, 'benzaldehyde, monoalkylsubstituted benzaldehydes such as o-tolualdehyde, m-tolualdehyde,'ptolualdehyde and corresponding ethyl-, propyland -butylbenzaldehydes,dialkyl substituted benzaldehydes such as 2,5-dimethyl benzaldehyde, 3,5dimethylbenzaldehyde, 2,6-dimethylbenzaldehyde, etc. and correspondingdiethyl-, dipropyland dibutylbenzaldehydes, monoalkoxy substitutedbenzaldehydes such as m-methoxybenzaldehyde, o-methoxy-benzaldehyde,p-methoxy-benzaldehyde and corresponding ethoxy-, propoxyandbutoxy-benzaldehydes, dialkoxy substituted benzaldehydes such as3,4sdimethoxy-benzaldehyde, 2,5 dimethoxy benzaldehyde, etc. andcorresponding diethoxy-, d'ipropoxyand dibutoxy-, benzaldehydes,'vanillin, isovanillin, piperonal, the carboxy-benzaldehydes such as-o-aldehydo-benzic acid, p-aldehydo-benzoic acid, etc. and sodium andpotassium salts thereof, the sulfo-benzaldehydes such asbenzaldehyde-m-sulphonic acid, benzaldehyde-o sulphonic acid, etc. andsodium and potassium salts thereof, acetamino-benzaldehydes such as-p-acetamino-benzaldehyde, etc., aminobenzaldehydes such asp-dirnethyland p-diethy1+aminobenzaldehydes, chlorobenzaldehydes such asp -chlorobenzaldehyde, o chlorobenzaldehyde, 3,5 dichlorobenzaldehyde,and the like to give the'corresponding 3-(w-hydroxyalkyl)-5-benzalhydantoins represented by the following general formula:

wherein n, m and X have the previously defined meanings.

The invention is illustrated further by the following examples.

Example ].Preparati0n of N-.B-hydr0xyethyl-N- carbethoxymethyl urea 65g. (0.5 mol.) of ethyl isocyanoacetate (O=C=N'CHz-'COOCzH5) was addedover a -minute interval to .a well-stirred mixture of 35 g. (approx. 0.6mol.) of ethanolamine in 500 cc. of dry benzenecoo'led externally byice. 'Heat was generated during the addition. The mixture was allowed tosit without stirring for'a few minutes after all reactants-were-added,1and a good crop of crystals was formed. These were washedwell with ether and airdried. A yield of 90.7 g., M. P. 7173 C.equivalent to 95.5% of calculated theoretical was obtained of theproduct. Analysis of the product gave by weight 43.8% of carbon, 7.5% ofhydrogen and 14.4% of nitrogen compared with calculated theory for theseconstituents of 44.2%, 7.4% and 14.5%, respectively, indicating therebythat a substantially pure'N fi-hydroxyethyl-N- carbethoxymethyl ureahadbeen obtained.

-In place of the ethanolamine, in the above example, there can besubstituted an equivalent amount of propanolamine to giveN-y-hydroxypropyl-N'-carbetb.oxy-

methyl urea, or an equivalent amount of butanolamine to giveN-w-hydroxybutyl-N'-carbethoxymethyl urea.

Example 2.-Preparati0n of 3-(fl-hydr0xyethyl) hydantoin A mixture of 20g. of N-fi-hydroxyethyl-N-carbethoxymethyl urea prepared as described inExample 1 and 50 cc. of 6-normal hydrochloric acid was evaporated .byheat to a thick syrup. The liquid was then cooled 'in ice giving nearlya solid mass of slightly off-white crystals. This product was isolatedby filtration, recrystallized twice from absolute alcohol, washed withether and air-dried at 40 C. A yield of 7.4 g., M. P. 98 -101 C. wasobtained. Analysis of this product gave by weight 42.0% of carbon, 5.7%of hydrogen and 19.5% of nitrogen compared with calculated theory forthese constituents in 3-(fi-hydroxyethyl) hydantoin of 41.6%, 5.5% and19.4%, indicating thereby that the product was essentially pure 3-(8-hydroxyethyl) hydantoin.

By substituting for the N-B-hydroxyethyl-N-carbethoxymethyl urea in theabove example, an equivalent amount ofN-whydroxypropyl-N-carbethoxymethyl urea or an equivalent amount ofN-w-hydroxybutyl-N'-carbethoxymethyl urea, there is obtained thecorresponding 3- hydroxypropyl) hydantoin and 3-(w-hydroxybutyl)hydantoin.

Example 3.Preparati0n of 3-(B-hydr0xyethyl)-5-anisal hydantoin 22 g.(0.15 mol.) of 3-(fl-hydroxyethyl hydantoin prepared as described inExample 2, 21 g. (0.15 mol.) of anisaldehyde, 35 cc. of dry pyridine and15 cc. of diethylamine were refluxed together for 7.5 hours, thenallowed to stand at room temperature .for approximately 5 hours. Theheavy orange colored precipitate which formed was recrystallized twicefrom ethanol and dried in air at 40 C. The resulting yellow product hada melting point 'of 206-207 C. and by analysis contained by weight 59.8%of carbon, 5.2% of hydrogen and 10.5% of nitrogen compared withcalculated theory for these constituents of 59.5%, 5.3% and 10.7%respectively, indicating that the product obtained was essentially '3-(Bhydr0xyethyl)-5-anisal hydantoin having the structural .formula:

rag a...

In place of the "3-(fi-hydroxyethyl) hydantoin in the above example,there can be substituted an equivalent amount of 3- y-hydroxypropyl')hydantoin to give 3-( hydroxypropyD-S-anisa'l hydantoin or an equivalentamount of 3-(w-hydroxybutyl) hydantoin to give 3-(0-hydroxybutyl)-5-anisal hydantoin. Other of the .mentioned aldehydes suchas benzaldehyde and substituted benzaldehydes can also be used in theabove example to replace the anisaldehyde to give corresponding3-(hydroxyalkyl)-5-benzal hydantoins.

width poured into 2.5 liters of distilled water containing 500.

cc. of acetic acid. Excellent, slightly tan fibers were obtained. Thesewere washed in 3 liters of distilled water containing 250 cc. of aceticacid, and then in three successive distilled water washes. The resultingmaterial was air dried at 45 C. A yield of 11.0 g. of product wasobtained which on analysis gave values for carbon, hydrogen, nitrogen,methoxyl and carboxyl whichindi: cated that the polymeric productcontained approximately 0.43 mol. substitution of the hydantoin compoundper mol. of styrene-maleic anhydride employed. This result indicatesthat over 85% of the maleic anhydride groups in the copolymer hadreacted with the 3-(fl-hydroxyethyl)-5-anisal hydantoin to give aresinous light-sensitive polymer comprising essentially the recurringstructural unit:

CHaCHOH-OH 5H CrH4N--C=O E gno The product obtained in above Example 4was soluble in dioxane, dimethyl formamide and methyl Cellosolveacetate, but insoluble in methyl ethyl ketone. A 2% solution or dope ofthe product in dioxane was coated on a paper support, the coated paperthen exposed to a carbon are through a step density tablet under bothglass mentioned 3-hydroxyalkyl-5-anisal hydantoins for the 13(B-hydroxyethyl)-5-anisal hydantoin in the above Ex-- ample 4, othergenerally similar light-sensitive resinous polymers can be prepared, forexample, the reaction prod-' uct of the styrene-maleic anhydride withB-(y-hydroxypropyl)-5-anisal hydantoin or the reaction product of thestyrene-maleic anhydride with B-(w-hydroxybutyD-S- anisal hydantoin.

Also, as previously mentioned, the styrene-maleic anhydride copolymer inabove Example 4 can be substituted by any styrene-maleic anhydridecopolymer wherein the molar ratio of styrene to maleic anhydride comeswithin the ratio of from 1:1 to 3:1. Since the number of lightsensitivehydantoin groups present in the resinous-polymer product cannot exceedthe total number of maleic anhydride groups, it will be understood thatthe lightsensitivity of products prepared with molar ratios less than1:1 of maleic anhydride will decrease; accordingly.

By proceeding as set forth in the above description and examples, othergenerally similar light-sensitive resinous polymeric products can beprepared. For example, any of the mentioned copolymers of maleicanhydride with ethylene, isobutylene, vinyl carboxylic esters, alkylacrylates or alkyl methacrylates,'etc. can be reacted with any of thementioned reaction products of 3-(fi-hydroxyethyl) hydantoin or 3-(-hydroxypropyl) hydantoin or 3-(w-hydroxybutyl) hydantoin reactionproducts with benzaldehyde or various substituted benzaldehydes to giveresinous polymers characterized by becoming insoluble on exposure tolight and, therefore, suitable for preparing resist images forphoto-mechanical reproduction processes.

What I claim isr 1. A resinous ester copolymer comprising the m me ringstructural units:

, member selected from the group consisting of an atom of hydrogen, ahalogen atom, a phenyl group, a naphthyl group, a pyridyl group, a cyanogroup, a carbamyl group, a carboxyl group, an OCOR2 group, a -COORzgroup, an OR2 group, a --CONHR2 group, and a -CO-NRzRz group wherein R2represents an alkyl group of from 1 to 4 carbon atoms, and wherein xrepresents a member selected from the group consisting of an atom ofhydrogen, an atom of chlorine, an alkyl group" of from 1 to 4 carbonatoms, an alkoxy group containing from 1 to 4 carbon atoms, an acetaminogroup, a

carboxyl group, a sulphonic acid group, a CO-OR2 group, a -SO:R2groupand a '-NR2R2 group wherein R2 is as above defined.

2. A resinous ester copolymer comprising the recurring structural units:

(1) Amt-on biz-Occur in the molar ratio of from 0.5 :1 to 3:1 of unitsof (l) to units of (2). I

5. A resinous ester copolymer comprising the recurring structural units:

EEG-O on.

in the molar ratio of from '0.'5.1 to 3:1 of units of (1) to units of(2).

6. A resinous ester copolymer comprising the recurring structural units:

pound having the general formula:

CH1=$-R in the molar ratio of from 0.5 :1 to 3:1 of the said compound tomaleic anhydride, and wherein R represents a member selected from thegroup consisting of an atom of hydrogen and a methyl group, and R1represents a member selected from the group consisting of an atom ofhydrogen, a halogen atom, a phenyl group, a naphthyl group, a pyridylgroup, a cyano group, a carbamyl group, a carboxyl group, a OCOR group,a OR2 group, a CO-NHR2 group and a CONR2R2 group wherein R2 representsan alkyl group of from 1 to 4 carbon atoms, with a hydantoin compoundhaving the general formula:

II CH wherein n represents an integer of from 2 to 4, m represents aninteger of from 2 to 3 and X represents a member selected from the groupconsisting of an atom of hydrogen, an atom of chlorine, an alkyl groupof from 1 to 4 carbon atoms, an alkoxy group containing from 1 to 4carbon atoms, an acetamino group, a carboxyl group, a sulphonic acidgroup, a COOR2 group, an SO3R2 group and an NR2R2 group wherein R2 is asabove defined.

8. A process for preparing a resinous ester copolymer which comprisesheating at from 30 to C. a resinous binary copolymer containing maleicanhydride and styrene in the molar ratio of from 0.5 :1 to 3:1 ofstyrene to maleic anhydride with a hydantoin compound having the generalformula:

wherein n represents an integer of from 2 to 4, and R2 represents analkyl group of from 1 to 4 carbon atoms.

9. A process for preparing a resinous ester copolymer which comprisesheating at from 30 to 120 C. a resinous binary copolymer containingmaleic anhydride and styrene in the molar ratio of from 0.5:1 to 3:1 ofstyrene to maleic anhydride with 3-(,8-hydroxyethyl)-5- anisalhydantoin.

10. A process for preparing a resinous ester copolymer which comprisesheating at from 30 to 120 C. a resinous binary copolymer containingmaleic anhydride and styrene in the molar ratio of from 0.511 to 3:1 ofstyrene to maleic anhydride with 3-('y-hydroxypropyl)-5- anisalhydantoin.

11. A process for preparing a resinous ester copolymer which comprisesheating at from 30 to 120 C. a resinous binary copolymer containingmaleic anhydride and styrene in the molar ratio of from 0.521 to 3:1 ofstyrene to maleic anhydride with 3-(w-hydroxybutyl)-5- anisal hydantoin.

12. A process for preparing a resinous ester copolymer which comprisesheating at from 30 to 120 C. a resinous binary copolymer containingmaleic anhydride and styrene in the molar ratio of approximately 1:1 ofstyrene to maleic anhydride wth 3-(B-hydroxyethyD-5- anisal' hydantoin.

References Cited in the file of this patent UNITED STATES PATENTS2,527,821 Johnson Oct. 30, 1950

2. A RESINOUS ESTER COPOLYMER COMPRISING THE RECURRING STRUCTURAL UNITS: